Metalliferous azo-dyestuffs and process of making same



Patented Sept. 13, 1932 UNITEDSTATES rnrrz STRAUB Ann HANS MAY R, Fiansnn, SWiTZEItLAND,ASSIGNQRSAIO- FIRII or socrnry or CHEMICAL INDUSTRYIn BASLE, or BASEL, swrrznnnnnn METALLIFEROUS*AZO-DYESTUFFS Am)'Pnoo'nss or time tannin No Drawing. Application filed May 13, 1930,Serial No. 452,125, and in switz erland May'28, 1929.

This invention is an improvement in or modificationof that described inapplication Serial No. 397,140. I v t According to this inventionvaluable metalliferous dyestuffs which may contain one or more metalsare obtained byltreating an arm- ,dyestuii, derived from an unsulfonateddiazo compound containing lakeand salt-v forming groups inortho-position to the diazo-group and any desired unsulfonated couplingcomponent, with a group of insoluble compounds comprising oxides,hydroxides,

basic carbonates, carbonates and sulfides of metals adapted to formcomplexicompounds,

' the atomic weights ofwhichmetals lie above.

55. Suitablemetal agents are above all manganese, iron, cobalt, nickel,copper and ;Z11'1C.

- These agents yielding metal may zbe used dition of organic salts'oralkaline, neutral or singly or in mixtures, with or withoutthe adacidinorganic salts.

The metalliferous dyestuffs obtainable ac;

cording to this invention are particularly ap plicablein the manufactureof colored varnishes fast to ligl1t, which are derive clfrom celluloseesters or ethers or ral resins as bases. 7 v 7 V The following examplesillustrate the in.-

vention, the parts being by weight E'ivample 1 2.74 parts of thedyestuif from dia'zotized I 4-nitro-2-amino-l-phenol and resorcinol ofthe formula:

NO: OH

are dissolved in 250 parts of water to forma artificial and natu tic an;nis filtered,'washer anal dried at a moderate temperature; The product,is a dark brown powder, which dissolves in water to some extent to abrownsolution; in caustic soda solution easily to a deep brown solutionyellow solution. :In organic solvents it is, also freelysoluble ,itsdeep brown, solutionvin nitrocellulose varnish yields on metal surfacesvivid brown coatings ofyery good taste nessto light.

manganic oxide thereis obtained like manner a. reddish colored varnishI;WithFea'O a blackish brown ofvery good properties of fastness is Iobtained i and v with nickel ()X fi -QQv pared with thoseobtainedwithout such an addition, may have difierent properties in respect ofshade,soli1bility'and the like, I, b 2

v 6.57 parts 'ofthe dyestufl' from diazotized' methyl -v5epyrazolone ofthe formula.

By. using ferric V oxide 1 4-ch-lor'o 2-amino=1-phenol and l phnyl-3-are boiledin 500 parts ofwiter then heated'to boiling fo'r. some time ina' reflux apparatus with" a suspension of' freshly precipitated 55 andin concentrated sulfuric acid-to a brown I with 1.3 part of. nickel.

ferric hydroxide corresponding in quantity with 1.2 part of iron. Aftercooling, the dyestuif which has separated is filtered, washed and driedat a moderate temperature.

1y soluble in water,somewhat soluble in caustic soda, solution to abrown yellowsolution and soluble in concentrated sulfuric acid to a Vbrown red solution. Its greenish yellow solution-1n nitrocellulosevarnish and other varnlshes yields on metal surfaces greenish yel lowcoatings which are thoroughly fast to.

light.

Example 3 5.48 parts of the dyestufi' from diazotized 4nitro-2-amino-Lphenol and resorcinol of the formula are dissolved hot in400 parts of water and the solution is heated to boiling in arefluxapparatus for some time with freshly precipitated nickel hydroxidecorresponding in quantity After cooling, the metal compound isprecipitated by neutralization with acetic acid, filtered, washed anddried at a moderate temperature. The red brown powder is solublesparingly in water, 'freely in caustic soda solution to a brown redsolution andin concentrated sulfuric acid to a brown yellow solution. Inorganic solvents it dissolves freely to a brown yellowsolution and itssolution; in commercial varnishes yields brownish yellow coatingsofgoodfastmess to light.- i

E wample Qt 5.97 parts of the dyestufl from diazotized4chloro-2-amino-1-phenol and fi-naphthol of the formula V a I are boiledin 500 parts of water and heated to boiling for some time in a refluxapparatus The mixed complex containing copper and iron made from theabove azo-dyestuif dissolves in nitrocellulose varnish with a brown Whendry it is an olive brown powder, very sparing- 7 Etcamplc 5 I274: partsof the dyestuff from diazotized 4-nitro-2 amino-l-phenol andresorcin'ol' of the formula N ME are dissolved hot in 250 parts of waterand the solution, after addition of 5 parts of calcined sodium sulfate,is heated to boiling for some-time with a quantity of freshlyprecipitated and neutral ferric hydroxide suspension corresponding with0.6 part of iron. After cooling, the complex metal compound iscompletely precipitated by neutralization with acetic acid, filtered,washedand dried at a moderate temperature. The dyestuff is a brownpowder which is sparingly soluble in water, freely in caustic sodasolution to a deep brown solution and in concentrated sulfuric acid to abrown yellow solution. Its brown solution in nitrocellulose varnishyields on metal surfaces Vivid brown coatings very fast to light.

' Similar metal compounds are produced when in place of sodiumsulfate-as the added salt, there is used another neutral salt, such ascommonsalt or sodium thiosulfate, or an alkaline salt, such as sodiumacetate or sodium sulfite, or an acid salt, such as primary sodiumphosphate or sodium bisulfite.

Under analogous conditions other dyestuif combinations of this kind canbe converted into the corresponding complex metal com pounds.

Instead of preparingthe necessary metal hydroxide by washing it neutralafter precipitation, it is equally possible to operate directly with theprecipitation mixture obtained by precipitating a solution of therequired metal salt with the theoretically necessary proportionofcau'sticsoda solution, such mixture necessarily containing besides thehydroxide of the metal the sodium-salt of the acid of the metal salt.

Example 6' i 5.97 parts of the dyestufi from diazotized4-chloro-2-amino-l-phenol and ,B-naphthol of the formula areboiled in500 parts of water and5 parts of tertiary sodium phosphate (NmPOy- 1OHO) and then heated to boiling for some I time in a reflux apparatus witha quantity of freshly precipitated and neutral ferric hydroxidesuspension corresponding with 1.2 part of iron. After cooling,'thedyestuff which has separated is filtered, washed, dried at a moderatetemperature. Its dark brown iron compound dissolves very sparingly inwater and caustic soda solution and in concentrated sulfuric acid to ared violet solution. Its deep brown solution in nitrocellulose Varnishyields on metal surfaces dark brown to black coatings of very goodfastness to light.

If, instead of the sodium phosphate another alkaline salt, such assodium bicarbonate or sodium acetate, is used analogous products areobtained.

With nickel carbonate, with or without addition of inorganic or organicsalts, products are obtained which color varnishes orange tints fast tolight.

In similar manner there is obtained, for example, from the 'dyestuff4-nitro-2-amino-1- phenol resorcinol withiron carbonate abrown lake. I

. Example 7 2.63 partsof the-dyestufi from diazotized4-chloro-2-amino-l-phenol and resorcinol of concentrated sulfuric acidto a brown yellow solution. Its brown yellow solution in nitrocellulosevarnish yields on metal surfaces brownish yellow coatings.

E wample 8 2.63 parts of the dyestufi from diazotizedl-chloro-Q-amino-1-phenol and resorcinol of the formula QM Qa are boiledin 250 parts of water and the mixture is heated to boilingin a refluxapparatus for some time with a freshly precipitated and neutralsuspension of cobalt sulfide corresponding with 0.65. part of cobalt.After cooling, the cobalt compound is precipitated by addition of somecommon salt, washed and dried at a moderate temperature; It is a darkbrown powder which dissolves inwater to a red solution, in caustic sodasolution to a deep red solution and in concentrated sulfuric acid to abrown yellow solution. Its bluish red solution in nitrocellulosevarnishyields on metal surfaces red coatings.

By treatment with cobalt sulfide with addition of 5 parts of sodiumacetate there is obtained a cobalt compound of essentially the sameproperties. 7

In place of sodium acetate other salts of alkaline reaction may be usedwith the same result, such as sodium bicarbonate, or tertiary sodiumphosphate also neutral salts, such as sodium sulfate; or acid salts,such as primary sodium phosphate or, finally, sodium carbonate, causticsoda solution or sodium sulfite and other alkalies.

'What we claim is I 1-. Process for the manufacture ofmetal compounds ofunsulfonated'azo-dyestuffs,' consisting in treating azo-dyestufl'sobtainable by coupling unsulfonated diazo components of the benzeneseries containing lakeforming groups in ortho-posltion tothe d1a-zogroup, with. unsulfonated coupling comp'o nents of the benzene,naphthalene and pyrazo lone series, with a memberof the group of metalcompounds consisting of the oxides, hydroxides, basic carbonates,carbonates and sulfides of such metals capable of producing complexmetal compounds with the lake-.

forming groups of the azo-dyestuffs the atomic weights of which metalslie above 55.

2. Process for the manufacture of metal compounds of unsulfonatedazo-dyestufi's, consisting in treating azo-dyestufis, obtainable bycoupling unsulfonated ortho-hydroxy-diazo compounds of the benzeneseries with unsulfonated coupling components of the benzene,naphthaleneand pyrazolone series, with a member of the group of metalcompounds consisting of the oxides, hydroxides, basic carbonates,carbonates, carbonates and' sulfides of such metalscapable of producingcomplex metal compounds with the lake forming groups of theazo-dyestuffs the atomic weights of which metals'lie above 55. a

3. Process for the manufacture of metal compounds of unsulfonatedazo-dyestuffs, consisting in treating azo-dyestufl's, obtain able bycoupling unsulfonated ortho-hydroxydiaZo compounds of the benzene serieswith unsulfonated coupling components of the benzene, naphthalene andpyrazolone series with'a member of the group of metal compoundsconsisting of the oxides, hydroxides, basic carbonates, carbonates andsulfides of metals the atomic weight of' which metals range between.55and 66..

consisting in treating azo-dyestufis, obtainable by couplingunsulfonated ortho-hydroxy-diazo compounds of the benzene series withunsulfonated coupling components of the benzene, naphthalene andpyrazolone series, with a member of the group of metal compoundsconsisting of the oxides and hyclroxides of metals the atomic weights ofwhich metals range between 55 and .66.

5. Process for the manufacture of metal compounds of unsulfonatedazo-dyestuffs, consisting in treating azo-dyestuffs, obtainable bycoupling unsulfonated ortho-hydroxy-diazo compounds of the benzeneseries with unsulfonated hydroxy compounds of the "benzene andnaphthalene series capable of coupling, with a member of the group ofmetal compounds consisting of the oxides and hydroxides of metals theatomic weights of A which metals range between 55 and 66.

6. Process for the manufacture of metal compounds of unsulfonatedazo-dyestuffs, consisting in treating a zo-dyestuffs, obtainable bycoupling unsulfonated ortho-hydroxy-diazo compounds of the benzeneseries with unsulfonated hydroxy compounds of the benzene andnaphthalene series capable of coupling, with a member of the group ofmetal compounds consisting of the hydroxides of metals the atomicweights of which metals range between 56 and 63.6.

7. Process for the manufacture of an azodyestuff containing iron,consisting in treating an azo-dyestufi', obtainable by coupling4-chloro-2-diazo-1-phenol with B-naphthol, with any one of thehydroxides ofiron.

8. As new products the metal compounds of azo-dyestufis which correspondwith the azo-dyestuffs of the general formula wherein R is anunsulfonated andv uncarboxylated benzene radicle, R is an unsulfonatedand uncarboxylated benzene, naphthalene or pyrazolone radicle, and thehydroxy group stands in ortho-position to the azobridge, which metalcompounds are obtained by treating these azo-dyestufis with a mem- T berof the group of metal compounds consisting of the oxides, hydroxides,basic carbonates, carbonates and sulfides of such metals capable ofproducing complex metal compounds with the hydroxy groups of theazodyestuifs the atomic weights of which metals lie above 55, and whichproducts form, when dry, dark powders, soluble in many organic solventsand in the usual varnishes with various colors;

camera;

of azo-dyestufis' which correspond with the,

' azo-dyestuffs of the general formula. 4.. Process for the manufactureof metal v compounds of unsulfonatedv Yam-dyestuffs,

N=NRz oH wherein R is an unsulfonated and uncarboxylated benzeneradicle, R is an unsulfonated and uncarboxylated benzene, naphthalene orpyrazolone radicle, and the hydroxy group stands in ortho-position tothe azo-bridge, which metal compounds are obtained by treating theseazo-dyestuifs with a member of the group of metal compounds consistingof the oxides, hydroxides, basic carbonates, carbonates and sulfides ofmetals the atomic weights of which metals lie between 55 and 66, and.which products form, when dry, dark powders, soluble in many organicsolvents and in theusual varnishes with green-yellow, brown-yellow,brown, red and. black colors.

10. As new products the metal compounds of azo-dyestufi's whichcorrespond with the azo-dyestuffs of the general formula wherein R is anunsulfonated and uncarboxylated benzene radicle, R is an unsulfonatedand uncarboxylated benzene, naphthalene or pyrazolone radicle, and thehydroxy group stands in orthoposition t0 theazo-bridge, which metalcompounds are obtained by treating these azo-dyestuft's with a member ofthe group of metal compounds consisting of the oxides and hydroxides ofmetals the atomic weights of which metals lie between 55 and 66, andwhich products form, when dry, dark powders, soluble in many organicsolvents and in the usual varnishes with green-yellow, brown-yellow,

brown, red and black colors.

11. As new products the metal compounds of azo-dyestuifs whichcorrespond with the azo-dyest-uf'fs of the general formula wherein R isan unsulfonated and uncarboxylated benzene radicle, R is an unsulfonatedand uncarboxylated benzene, naphthalene or pyrazolone radicle and thehydroxy group of the benzene radicle R stands in ortho-position to theazo-bridge, which metal compounds are obtained by treating theseazo-dyestufis with a member of the group of metal compounds consistingof the oxides and hydroxides of metals the atomic weights of whichmetals lie between 55 and 66, and which products form, when dry, darkpowders, soluble in many organic solvents and in the usual varnisheswith brown-yellow,

brown, red and black colors. 9. As new products the metal compounds 12.As new products themetal compounds;

of azo-dyestufi's which correspond with the azo-dyestutfs of the generalformula N=NRa R1\OH H.

wherein R is an unsulfonated and uncarboxylated benzene radicle, R is anunsulfonated and uncarboxylated benzene, naphthalene or pyrazoloneradicle and the hydroxy group of the benzene radicle R stands inortho-position to the azo-bridge, which metal compounds are obtained bytreating these azo-dyestufis with a member of the group of metalcompounds consisting of the hydroxides of metals the atomic weights ofwhich metals lie between 56 and 63.6, and which products form, when dry,dark powders, soluble in many organic solvents and in the usualvarnishes with brown-yellow, brown, red and black colors.

13. As new products the metal compounds of azo-dyestufis whichcorrespond with the azo-dyestufts of the general formula wherein Rstands for an unsulfonated and uncarboxylated benzene radicle, R for anunsulfonated and uncarboxylated naphthalene radicle, and the hydroxygroup of the benzene radicle R stands in ortho-position to theazobridge, which metal compounds are obtained by treating theseazo-dyestuiis with a member of the group of metal compounds consistingof the hydroxides of metals the atomic weights of which metals liebetween 56 and 63.6, and which products form, when dry,

dark powders, soluble in many organic solvents and in the usualvarnishes with brown and black colors.

14. As a new product the iron compound of the azo-dyestulf whichcorresponds with the azo-dyestufl' of the formula which compound isobtained by treating this azo-dyestufi' with any one of the hydroxidesof iron, the product thus obtained forming, when dry, a dark powder anddissolving in many organic solvents and in the usual varnishes withblack color.

In witness whereof we have hereunto signed our names this 3rd day ofMay, 1930.

FRITZ STRAUB. HANS MAYER.

